Halogenated extreme pressure lubricant



to tho oooioooycl-ic nuclei.

' Patented Mai. 1941 liotiu lllit OFFICE oi @hlo l lo liioottioigi hoollootioin iillotolioi lit ooitoi ltoi til-WW m Wi low with; iuveutiou oeiotes to iuhr-iwuts ii to title iuothotl oi. preparing and using the 12, mild to more ooitieulorly ooncemodl with lubriooiito howling extreme pressure chmmtoristios. M lit is well known that mineral lubriootiuo oiio com to improved to adding thereto halogenated.

ox'omotic hydroooirhons one! compounds in Wluoh liydroueu in the ommwtic nucleus is sulootitut lu ohloi'ino. Many halogenated oli ohotic hydro-- iii owl-boos and compounds in general vo n louuoi to he wvw hecauoe ouoh oom ooumls hydrolyze readily in mutual; with watw' looming ooidi which oormdes the metal our! ll hove tiiooovoi-eci that oertaln chlorinated ostero it iiuii kotouos, wherethe ohlooine is attached to o.

ooitoou which to loowted hetwoen m mmtocted by oomooiulc, stable, oromatic or other oarbocyclio nuclei ore not only not corrosive hut are more ootivo than the halogenated or omotim. iSuo-h m oom-pounclo have the ability to import to mineral iuhtiootluo oilsv increased oliiness, omngth I ouol eiotreme pressure characteristics.

flhe compounds which I have discovered to be suitable are those of the type i W H: Ito

R .r-c 0-6Z-W unit 7 lHa. i-ia pm R fl-"C 0--G(:-R

iu uvhiioli ll oucl it oil-o mu ooiuio otohlo, itiil motto or othoo ooi hooyiclio mioiel olthor-tlio Ht Wt oi." oiiii'ooeut, il is the ohoiootoo uii ouo touml to esters, U0 is the bivalent ketone orouo tit louool imtouot, (3 represents on oliohatio W loom l fltd'iwl either saturated or unsatteol hovloo my number (n) of cartoon atoms and Ho tome-omits a halogen united to one or more all uhotio carbon atoms which are linked between These compounds are oir to those disolosed in the co-pending SIP- pliootion of William Arwhittier, Ber. No. 180,- lt'l, but distinguish Irom the compounds thereto disclosed by containing; the characteristic COO to outer group or C0 ketone group.

llmmples oi oompouncio which are suitable tor use ore oiohlor phenyl ethyl oinnamuto, tetroon :omyl oinnamate,dichlor oyl ooetouliouone, tetmchlor dibenzylidene motono ond m ootochlor moinnomylicleneaoetoue. The liologeu mow he odded directly to the carbon in those oomtiouuds, which an, unsaturated or may room-to tho hydrogen in. those oompoiio which oi'o iotutotool" in the cute of unsotm'otool ooiuoouuolo, i'iuioitou moy limited to tho oorloou toy oitoot otltlitiou atoll loo oulootitut-iouol the hywlrogoo.

ilouoiui o :i tho oomitor tho number of ohloo iuo oto ilool to tho Whom, tho greotor lo tho oootivouooo oi tho oomoouutl as, E. P.

till-ti g to Hluotioto moi'o olwi'lo tho noturo of the oouiouo with which thio invention to oomooi'uotl, tho lolloo moo formulae are H H 0 H H W w Diolilmrphenylethylto lo u u u u o u u u ot-o-iiii o in h on in titititi liotaehlordicionomyllcieno ao'otona u u o u H 'iotmohlor derivative oi pom pom clibemylidone acetone u u o u t t t t it on its 1'21 ti 'iotroohlor clionisylliione oootoioo v o oioooootoo oomoouuclo ooouootioo with otooiuht miuoirol tum-looting oils fi -Q or in connection with oils; which hove been lolenu-w with other reogeuto to imm-ovo tho iuhr'iwxt lug oriotioo omit us for example, olooo ohm-well or suifurized and ohosphorized lubricents. (me method of preporlng a ph-osphorioecl I lubricant is as follows: No. 1 lord oil is host We with of phosphorous oxychloride at 17mm, to 200 F. for minutes. During this time only a 1 slight darkening oi the oil 006m. The temperature is then slowly increased to 2'l'5 F. in order to drive remoining phosphor-om omm -m to 7 A block oludze l in the amount oi apprommately 5% of the oil, otter it has been uocanteu from the sludge, l3 iilendotl with of luhmiowtiuo oil having the following charactonistioo': 59 Gravity no.1. l 21-23 mosh "AF" oooooo Fire "F" ooo-oio Wooooitw, oo rhoit oi; till" i lofi-loii I ooio m;.=...t oo-uo i out be used inl to f I have found that when small quantities of halogenated compounds of the nature of those above described are incorporated in a blend of mineral lubricating oil with a sulfurized and phosphorized fatty oil base such as that disclosed in the application of Whittier et al, Ser. No. 55,200, the extreme pressure characteristics of such lubricants can be materially improved. A number of tests have been made on straight lubricants blended with halogenated compounds of the nature of those above set forth and on lubricants blended with sulfurized and phosphorized base together with halogenated compounds, the results of which are given in Table III. In these tests the straight mineral oil used was a blend to approximately 8. A. E. viscosity of the following oils:

In those tests in which a mineral oil was blended with sulfurized-phosphorized base and/ or chlorinated compound, the lubricating oil before blending had the following characteristics:

Table II A. P. I. gravity 18-20 Flash F 380-400 Fire F" 430-450 Vis. at 130 F. (Say. Univ.) 460-500 V15. at 210 F. (Say. Univ.) 90-95 Pour point; F 0

This oil was blended with sulfurized phosphorized base in the proportion of 82% of ollto 18% of base. The sulfurized-phosphorized base was made in the following manner: A homogeneous mixture of 570 pounds of Gulf Coast pale oil having a Saybolt Universal viscosity at F. of 200 seconds and a pour point of 20 to -25 F. and 55 pounds of sulfur chloride was prepared in a cold state. This mixture was added to 9,581 pounds of prime lard oil contained in arr enclosed steam jacketed kettle. The mixture was heated to 275 F. while being vigorously agitated. At this point the steam was shut off and 814 pounds of flowers of sulfur were sifted into the contents of the kettle over a period of approximately two hours. The contents of the kettle were vigorously agitated during this entire period. At the end of the two-hour period the temperature had dropped to 265 F. The steam was again turned on and the contents of the kettle heated to approximately 300 F. when the steam was turned ofi. Agitation was continued for a period of approximately 7% hours after the addition of the sulfur. During this period the temperature rose from 300 to 344 F. during the first three hours indicating that an exothermic reaction was taking place. The temperature during the 7 -hour period was not permitted to drop below 320 F. and it was found that it was unnecessary to use any further heat to maintain this temperature after the mixture had been initially heated to 300 F.

The sulfurized material was then cooled to a temperature of 220 to 230 F. by circulating the material through cooling coils and back to the kettle. When this temperature had been reached, d4 pounds of phosphorous sesqui-sulfide was added slowly over a period of hour of continuous agitation. The steam was again turned on at such times as was necessary to maintain the temperature at 220 to 230 F. After the addition of phosphorous sesqui-sulflde, agitation was continued for a period of approximately five hours while the temperature was maintained at 220 to 230 F. At the end of this period the contents of the kettlewere immediately cooled to F. by circulation through the exteriorly located cooling coils and pumped to storage.

The following is a table of results obtained:

Table III Halogsnated compounded added Adam Timken test 8. Lubricant used for blend at 1,000 R. P.

Pressure i 43 ON chlorine 310 Failed to hold starting load.

4 All of the lubricants named Sui-Plies. base blend" are composed of 82% mineral oil and 18% of sulfurized and phosphorized fatty oil.

The tests were made on the machine recommended as a tentative standard by the Society of Automotive Engineers for testing extreme pressure lubricants and on the Timken wear and lubricant tester. Both of these machines are Widely recognized as extremepressure type lubricant testing devices. 1

As shown above, the sulfurized-phosphorized lubricant without the addition of a chlorine compound, withstood a load of only 90 pounds on the S. A. E. machine but when small amounts of the chlorinated compounds were added, the load could be increased to over 300 pounds, although the chlorinated compounds when blended in small quantities with straight mineral oil tested only approximately 16,000 lbs. per sq. in. on the in"; machine and 90 lbs. on the S. A. E. ma

' chine. The E. 1?. characteristics of a phosphoriaed or a suIfurized-phosphorized lubricant as determined by the Timken machine, are not appreciably altered by addition of the halogen compound while greatly increasing the film strength and lit. P. characteristics of the lubricant as measured by the S. A. E. machine. The Timken test results of the sulfurlzed phosphorized lubricant blended with a chlorine compound are the same as the unblended material within the limit of accuracy of the testing machine. Corrosion tests made in the presence of water indicate that the halogenated compound may be introduced into the lubricant without rendering it corrosive.

Although I do not wish to be limited to the addition of any particular amount of the halogenated compound to the lubricant, I prefer to use from approximately 1% to 10% in connection with lubricants to be used where E. P. characteristics are important. Where the compound is added to improve the oiliness and film strength,

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Bill

till

as for example, in motor oil, the amount added may range from a fraction of 1% to approximately 5%. The upper limit of has been ed only because with the methods of testing now available, it has been found that maximum results can be obtained by adding this amount. ere is no reason, however, why quantities in crease of 10% may not be used.

ad of adding the halogenated compound ectly to the oil, it may be separately led into the particular mechanism to be lubricated and mixed in situ with the lubricating oil.

it has also been found that materials within the scope, of this invention containing a phosphorlzed or sulfurlzed and ph'osphorized lubricent and chlorinated esteror ketone of the class previously described, are excellent cutting fluids and are also well adapted to be used in drawing, grlndifi'g and burnishing operations. They may used straight, blended with mineral oil and/or emulsified with water.

What I claim is:

l. A lubricant comprising mineral lubricating oil and a compound selected from the group 01' ogcnated ketones or the type Ha. Ha

and halogenated esters of the type Ha Ha ndoootna' in which R and R are non-acidio.stable, oarycllc radicals either the same or different, CO d 000 are the characteristic ketone and ester groups. C is an aliphatic chain having any ulcer (n) of carbon atoms and the halogen (Ha) is linked to carbon in the aliphatic chain.

2. Method of lubricating relatively moving metallic surfaces which comprises maintaining between the surfaces and chemically reacting therewith a quantity of a compound selected from the group of halogenated ketones of the type Ha Ha nonoocma' and halogenated esters of the type Ha Ha a inooodnn' in which R and R are non-acidic, stable, carbocyclic radicals either the same or difi'erent, CO and COO are characteristic ketone and ester groups, C is an aliphatic chain having any number (n) of carbon atoms and the halogen is linked to carbon in the aliphatic chain.

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3. A lubricant in accordance with claim 1 to which has been added sulfurized and phosphorized fatty oil.

4. .A lubricant comprising a compound selected from the group of halogenated ketones of the p Ha Ha m imotuR' and halogenated esters of the type I Ha Ha in which R and R are non-acidic, stable, oarstam na and halogenated esters of the type Ha Ha RL NC 002MB in which R and R are non-acidic, stable, carbocyclic radicals of either the same or different, CO and CO0 are the characteristic ketone and ester groups, C is an aliphatic chain having any number (n) of carbon atoms and the halogen is linked to carbon in the aliphatic chain, to which has been added phosphorlzed fatty oil.

7. A lubricant comprising mineral lubricating oil and a'halogenated ester of the type in which R and R are non-acidic, stable, carbocycllc radicals, CO0 is the characteristic carban and oxygen'group round in esters, C is an aliphatic chain having any number (n) of carbonv atoms and the halogen is linked to carbon in the aliphatic chain.

8. A lubricant comprising mineral lubricating oil and a halogenated ketone of the type Ha Ha admit-11' in which R and R are non-acidic, stable. carbocyclic radicals, CO is the characteristic carbon and oxygen group found in ketones, C is an aliphatic chain having any number (n) of carbon atoms and the halogen is linked to carbon in the aliphatic chain.

9. Method of lubricating relatively moving metallic surfaces which comprises maintaining between the surfaces and chemically reacting therewith a quantity of a halogenated ester of the t p Ha He 1 in which R and R are non-acidic, stable, carbocyclic radicals, CO0 is the characteristic carban and oxygen group found in esters, G is an aliphatic chain having any number (n) oi carbon atoms and the halogen is linked to carbon in the aliphatic chain.

10. Method of lubricating relatively moving metallic surfaces which comprises maintaining between the surfaces and'chemically reacting therewith a quantity of a halogenated hetone of the type Ha Ha m zncohm in which it and R are non-acidic, stable, carbccycllc radicals, CO is the characteristic carbonand oxygen group found in ketones, C is an aliphatic chain having any number (n) of carbon atoms and the halogen is linked to carbon in the aliphatic chain.

ii. A lubricant comprising a halogenated .7 ester of the type ncncoobm' in which R and R are non-acidic, stable, carbocyclic radicals, C00 is the characteristic carbon and oxygen group found in esters, 2 is an aliphatic chain having any number (n) 01 car bon atoms and the halogen is linked to carbon in the aliphatic chain, to which has been added phosphorized fatty oil.

13. A lubricant comprising a halogenated ketone of the type I Ha Ha RJLCOhR in which R and R are non-acidic, stable, carbccyclic radicals, CO is the characteristic caricon and oxygen group found in ketones, C is an aliphatic chain having any number (n) or carbon atoms and the halogen is linked to carbon in the aliphatic chain, to which has been added sulfurized and phosphorized fatty oil.

it. A lubricant comprising a halogenated iretone of the type Ha Ha nbmodm' in which R and R are non-acidic, stable, carbocyclic radicals, CO is the characteristic carbon and oxygen group found in ketones, C is an aliphatic chain having any number (n) of carbon atoms and the halogen is linked to carbon in the aliphatic chain, to which has been added phosphorized fatty oil.

l5. A lubricant comprising mineral lubricating oil and tetrachlorcinnamyl cinnamate.

16. A lubricant comprising mineral lubricating oil and dichlorcinnamyl acetophenone.

1'1. A lubricant comprising mineral lubricating oil and chlorinated dibenzylidene acetone.

18. A lubricant in accordance with claim and containing sulfurized and phosphorized fatty oil.

19. A lubricant in accordance with claim 16 i and containing sulfurized and phosphorized fat- NORMAN D. WILLIAMS. 

